WO2017010517A1 - Composition antisalissure, feuille antisalissure et procédé de production d'une feuille antisalissure - Google Patents

Composition antisalissure, feuille antisalissure et procédé de production d'une feuille antisalissure Download PDF

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WO2017010517A1
WO2017010517A1 PCT/JP2016/070700 JP2016070700W WO2017010517A1 WO 2017010517 A1 WO2017010517 A1 WO 2017010517A1 JP 2016070700 W JP2016070700 W JP 2016070700W WO 2017010517 A1 WO2017010517 A1 WO 2017010517A1
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component
antifouling
general formula
alkyl group
mol
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PCT/JP2016/070700
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English (en)
Japanese (ja)
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麻貴 廣永
宮田　壮
小野　義友
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リンテック株式会社
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Priority to JP2016564346A priority Critical patent/JP6111004B1/ja
Priority to EP16824497.8A priority patent/EP3323865B1/fr
Priority to US15/744,464 priority patent/US20180201796A1/en
Priority to CN201680041456.XA priority patent/CN107849394B/zh
Priority to KR1020187001094A priority patent/KR102632023B1/ko
Publication of WO2017010517A1 publication Critical patent/WO2017010517A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1675—Polyorganosiloxane-containing compositions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1681—Antifouling coatings characterised by surface structure, e.g. for roughness effect giving superhydrophobic coatings or Lotus effect
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1687—Use of special additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups

Definitions

  • the present invention relates to an antifouling composition, an antifouling sheet having an antifouling layer formed from the antifouling composition, and a method for producing the same.
  • a molded product such as a mirror, a glass container, or a glass decorative article does not adhere to the surface such as water droplets, scratches, and dirt.
  • the surface of such a molded product is provided with water repellency and antifouling properties by coating with a film made of an antifouling substance, or by applying an antifouling sheet. Yes.
  • Patent Document 1 discloses a substrate such as glass by a laminate having a base layer formed of an inorganic compound and a water-repellent film that covers the surface of the base layer and is formed of a fluorine-containing compound.
  • a water-repellent film-coated article coated with a material is disclosed.
  • the water-repellent coated article described in Patent Document 1 has a water-repellent film formed from a fluorine-containing compound, it is not preferable from the viewpoint of environmental protection.
  • the antifouling sheet is exposed to a risk that the surface of the antifouling layer is damaged by contact with other substances. Even if it is a fine flaw such as an abrasion, it can be a factor that not only obstructs the field of view but also makes it difficult for water droplets attached to the antifouling layer surface to slide down.
  • dirt can be easily attached, or the attached dirt can be difficult to remove. And as a result, there exists a problem that the antifouling property of an antifouling layer falls. Therefore, the antifouling layer imparting water repellency and antifouling properties is required to have a higher surface hardness and more excellent friction characteristics. Furthermore, the antifouling layer is also required to have a good surface state and curability.
  • the present invention provides an antifouling composition that has a good surface state and curability, has good water repellency and water sliding properties, and can be a material for forming an antifouling layer having a high surface hardness and a low friction coefficient, and It aims at providing the antifouling sheet
  • the present inventors include an antifouling property comprising a tetrafunctional silane compound having a specific structure, a trifunctional silane compound having at least two specific structures, and a metal catalyst, and containing each component so as to satisfy a specific condition.
  • the present inventors have found that a composition can solve the above-mentioned problems and completed the present invention. That is, the present invention provides the following [1] to [14].
  • An antifouling composition containing the following components (A) to (D) and satisfying the following conditions (I) and (II):
  • R 1 represents an alkyl group having 1 to 6 carbon atoms
  • X 1 represents a halogen atom.
  • R 1 and X 1 there are a plurality the plurality of R 1 and X 1 are also identical to each other or may be different.
  • p represents an integer of 0 to 4.
  • R 2 represents an alkyl group having 6 to 14 carbon atoms.
  • R 3 represents an alkyl group having 1 to 6 carbon atoms, and
  • X 2 represents a halogen atom. If R 3 and X 2 there are a plurality, the plurality of R 3 and X 2 are either identical to one another or may be different.
  • q represents an integer of 0 to 3.
  • Component (D) Metal catalyst condition (I): Ratio of molar amount of component (A) to molar amount of component (B) [(A) / (B)] (molar ratio) is 1.4 or more ( II): Ratio of molar amount of component (B) to total molar amount of component (B) and component (C) [(B) / ⁇ (B) + (C) ⁇ ] (molar ratio) is 0.020. [2] The content of the component (D) is 0.010 mol% or more and 50.000 mol% or less with respect to 100 mol% in total of the components (A), (B) and (C).
  • the antifouling composition according to [1] above.
  • An acid catalyst which is the component (E) is further included, and the content of the component (E) is 0.010 with respect to 100 mol% in total of the components (A), (B) and (C)
  • the antifouling composition according to any one of the above [1] to [4], wherein the antifouling composition is at least mol% and at most 1.000 mol%.
  • the above component (E) is at least one selected from the group consisting of hydrochloric acid, phosphoric acid, acetic acid, formic acid, sulfuric acid, methanesulfonic acid, odoric acid, p-toluenesulfonic acid, and trifluoroacetic acid.
  • the total content of component (A), component (B), component (C), component (D) and component (E) in the antifouling composition is 100 in total.
  • the antifouling sheet according to the above [8] which has the antifouling layer on a substrate.
  • the antifouling sheet according to the above [8] wherein the antifouling layer has a structure sandwiched between two release materials.
  • Step (1) Step (A) for preparing an antifouling composition containing the following components (A) to (D) and satisfying the following conditions (I) and (II): Component (A): Si (OR 1 ) p (X 1 ) 4-p (a) [In the general formula (a), R 1 represents an alkyl group having 1 to 6 carbon atoms, and X 1 represents a halogen atom. When R 1 and X 1 there are a plurality, the plurality of R 1 and X 1 are also identical to each other or may be different. p represents an integer of 0 to 4.
  • R 2 represents an alkyl group having 6 to 14 carbon atoms.
  • R 3 represents an alkyl group having 1 to 6 carbon atoms, and
  • X 2 represents a halogen atom. If R 3 and X 2 there are a plurality, the plurality of R 3 and X 2 are either identical to one another or may be different.
  • q represents an integer of 0 to 3.
  • Component (D) Metal catalyst condition (I): Ratio of molar amount of component (A) to molar amount of component (B) [(A) / (B)] (molar ratio) is 1.4 or more ( II): Ratio of molar amount of component (B) to total molar amount of component (B) and component (C) [(B) / ⁇ (B) + (C) ⁇ ] (molar ratio) is 0.020.
  • Step (2) Step of applying antifouling composition on substrate or release material and drying to form antifouling layer [14] Antifouling obtained by the production method according to [13] above Dirty sheet.
  • the antifouling composition can be a material for forming an antifouling layer having a good surface condition and curability, good water repellency and water slidability, and having a high surface hardness and a low coefficient of friction.
  • seat which has the antifouling layer formed from the said antifouling composition, and its manufacturing method can be provided.
  • the antifouling composition of the present invention comprises a tetrafunctional silane compound represented by the general formula (a) as the component (A), a trifunctional silane compound represented by the general formula (b) as the component (B),
  • the (C) component includes a trifunctional silane compound represented by the general formula (c), and the (D) component includes a metal catalyst so as to satisfy conditions (I) and (II) described later.
  • the antifouling composition of the present invention preferably further contains an acid catalyst as the component (E), and other additives other than the components (A) to (E) as long as the effects of the present invention are not impaired. It may contain.
  • the antifouling layer formed from the antifouling composition of the present invention has a good surface condition and curability, good water repellency and water sliding, and has a high surface hardness and a low coefficient of friction. It becomes.
  • the antifouling layer is formed by the condensation reaction between the silane compounds in the antifouling composition and the formation of a polymer.
  • the present inventors have used the component (B), which is a trifunctional silane compound having an alkyl group having a relatively large number of carbon atoms, for the structure of the polymer obtained by the reaction between the silane compounds. It was noted that the presence of an alkyl group (R 2 in the general formula (b)) in the unit derived from the component contributes to the improvement of water repellency.
  • an uncondensed silanol group in which the alkoxy group is hydrolyzed easily exists (hereinafter, both are also simply referred to as “uncondensed point”).
  • uncondensed point reacts gradually due to long-term outdoor exposure and the like, causing curing shrinkage, distortion occurs in the antifouling layer. As a result, the occurrence and progress of cracks are promoted, and the weather resistance of the antifouling layer may be lowered.
  • the present inventors also used the (C) component, which is a trifunctional silane compound having an alkyl group having a small number of carbon atoms, different from the (B) component, and used the alkyl group in the unit derived from the (C) component.
  • the unit derived from the component (B) which is considered to contribute to the improvement of water repellency, becomes sparse, it was considered that the water repellency is lowered.
  • the present inventors have confirmed that when only the component (C) is used, the friction coefficient increases and the friction characteristics are poor.
  • the present inventors also paid attention to introducing a unit derived from the component (A), which is a tetrafunctional silane compound that plays a role of a spacer, between units derived from the component (B).
  • a unit derived from the component (A) which is a tetrafunctional silane compound that plays a role of a spacer
  • the unit derived from the component (B) which is considered to contribute to the improvement of water repellency, becomes sparse.
  • the hydroxyl groups present on the surface of the antifouling layer increased, and the water repellency of the antifouling layer was likely to be greatly reduced.
  • the inventors of the present invention provide an antifouling layer that achieves both good water repellency and excellent surface hardness by satisfying the following requirements, and also exhibits good friction properties. It has been found that it can be formed. That is, about the alkyl group in the unit derived from the component (B) (R 2 in the general formula (b)) and the alkyl group in the unit derived from the component (C) (R 4 in the general formula (c)) , Each selected a specific number of carbons. Then, the component (A) was introduced so as to satisfy a specific condition (I) described later, and the component (B) and the component (C) were used together so as to satisfy a specific condition (II) described later.
  • the antifouling composition of the present invention contains a tetrafunctional silane compound represented by the following general formula (a) as the component (A).
  • Si (OR 1 ) p (X 1 ) 4-p (a) [In the general formula (a), R 1 represents an alkyl group having 1 to 6 carbon atoms, and X 1 represents a halogen atom. When R 1 and X 1 there are a plurality, the plurality of R 1 and X 1 are also identical to each other or may be different. p represents an integer of 0 to 4. ]
  • the alkyl group may be selected as R 1, for example, a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, s- butyl, isobutyl, t- butyl group, n- pentyl group, Examples thereof include an n-hexyl group, a neopentyl group, and a methylpentyl group. Among these, from the viewpoint of obtaining better curability, a methyl group, an ethyl group, or an n-propyl group is preferable, and a methyl group or an ethyl group is more preferable.
  • the alkyl group that can be selected as R 1 may be either linear or branched, but is preferably linear.
  • the halogen atom that can be selected as X 1 is preferably a chlorine atom, a bromine atom, or an iodine atom, and more preferably a chlorine atom.
  • (A) component it is preferable to contain the silane type compound whose p in the said general formula (a) is 4.
  • the content of the component (A) in the antifouling composition has a viewpoint of improving the curability of the antifouling layer formed from the antifouling composition, a viewpoint of obtaining a good surface state, and a high surface hardness.
  • the total of 100 mol% of the component (A), the component (B) and the component (C) is preferably 45.00 mol% or more, more preferably 55.00 mol% or more, and further preferably 65. It is 0.000 mol% or more, more preferably 75.00 mol% or more, and preferably 98.00 mol% or less, more preferably 96.00 mol% or less.
  • the said content can also be computed from the compounding quantity at the time of mix
  • the antifouling composition of the present invention contains a trifunctional silane compound represented by the following general formula (b) as the component (B) together with the component (A).
  • R 2 Si (OR 3 ) q (X 2 ) 3-q (b) [In general formula (b), R 2 represents an alkyl group having 6 to 14 carbon atoms. R 3 represents an alkyl group having 1 to 6 carbon atoms, and X 2 represents a halogen atom. If R 3 and X 2 there are a plurality, the plurality of R 3 and X 2 are either identical to one another or may be different. q represents an integer of 0 to 3. ]
  • the alkyl group that can be selected as R 2 has 6 to 14 carbon atoms. If the alkyl group has less than 6 carbon atoms, the water sliding angle increases and the water repellency tends to decrease. From such a viewpoint, the carbon number of the alkyl group is preferably 7 or more, more preferably 8 or more, and still more preferably 9 or more. When the carbon number of the alkyl group exceeds 14, the curability of the antifouling layer formed from the antifouling composition is inferior. In addition, as the carbon number of the alkyl group increases, the antifouling composition tends to gel, and the surface state of the antifouling layer formed from the antifouling composition tends to deteriorate. From such a viewpoint, the carbon number of the alkyl group is preferably 13 or less, more preferably 12 or less, and still more preferably 11 or less.
  • alkyl group that can be selected as R 2 examples include n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, and n-tridecyl group. N-tetradecyl group, methylpentyl group, pentylhexyl group, butylpentyl group, 2-ethylhexyl group and the like.
  • the alkyl group that can be selected as R 2 may be either linear or branched, but from the viewpoint of improving the curability and surface state of the antifouling layer formed from the antifouling composition.
  • the straight chain is preferable.
  • n-hexyl group, n-decyl group, n-dodecyl group and the like are preferable, and from the viewpoint of obtaining better water repellency, n-decyl group, Alternatively, an n-dodecyl group is preferable, and an n-decyl group is more preferable from the viewpoint of achieving a good balance between curability and surface state of the antifouling layer, surface hardness, and water repellency.
  • the alkyl group that can be selected as R 3 and the halogen atom that can be selected as X 2 are the same as the alkyl group that can be selected as R 1 and the halogen atom that can be selected as X 1 in the general formula (a). Is mentioned.
  • the component (B) preferably contains a trifunctional silane compound in which q in the general formula (b) is 3.
  • the content of the component (B) in the antifouling composition is preferably 0.30 mol% or more, more preferably with respect to 100 mol% in total of the components (A), (B) and (C). Is 0.40 mol% or more, more preferably 0.50 mol% or more, still more preferably 0.80 mol% or more.
  • the said content can also be computed from the compounding quantity at the time of mix
  • the antifouling composition of the present invention is an antifouling composition that satisfies the following condition (I) in the relationship between the component (A) and the component (B).
  • the [(A) / (B)] (molar ratio) is preferably 1.5 or more, more preferably 1.9 or more, still more preferably 2.1 or more, and even more preferably 2 .5 or more, more preferably 5.0 or more.
  • the [(A) / (B)] (molar ratio) is preferably 300.0 or less.
  • the [(A) / (B)] (molar ratio) is 300.0 or less, the presence ratio of the alkyl group represented by R 2 in the component (B) is prevented without being extremely reduced.
  • the antifouling layer formed from the fouling composition has better water repellency.
  • the [(A) / (B)] (molar ratio) is more preferably 200.0 or less, still more preferably 150.0 or less, still more preferably 100.0 or less, and still more preferably. Is 90.0 or less.
  • the antifouling composition of the present invention contains a trifunctional silane compound represented by the following general formula (c) as the component (C) together with the components (A) and (B).
  • R 4 Si (OR 5 ) r (X 3 ) 3-r (c) [In general formula (c), R 4 represents an alkyl group having 1 to 3 carbon atoms. R 5 represents an alkyl group having 1 to 6 carbon atoms, and X 3 represents a halogen atom. If R 5 and X 3 there are a plurality, the plurality of R 5 and X 3 are either identical to one another or may be different. r represents an integer of 0 to 3. ]
  • the alkyl group that can be selected as R 4 has 1 to 3 carbon atoms. When the carbon number of the alkyl group exceeds 4, the curability of the antifouling layer formed from the antifouling composition is inferior, and the surface hardness tends to decrease.
  • Examples of the alkyl group that can be selected as R 4 include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, and a methyl group or an ethyl group is preferable from the viewpoint of obtaining better water slidability. From the viewpoint of obtaining a higher surface hardness and a lower friction coefficient, a methyl group is more preferable.
  • the alkyl group that can be selected as R 5 and the halogen atom that can be selected as X 3 are the same as the alkyl group that can be selected as R 1 and the halogen atom that can be selected as X 1 in the general formula (a). Is mentioned.
  • the component (C) preferably includes a trifunctional silane compound in which r in the general formula (c) is 3.
  • the content of the component (C) in the antifouling composition has a viewpoint of improving the curability of the antifouling layer formed from the antifouling composition, a viewpoint of obtaining a good surface state, and a high surface hardness. From the viewpoint of obtaining, it is preferably 0.50 mol% or more, more preferably 0.80 mol% or more, further preferably 1 with respect to 100 mol% in total of the component (A), the component (B) and the component (C). It is 0.000 mol% or more, more preferably 1.30 mol% or more, and preferably 40.00 mol% or less, more preferably 38.00 mol% or less. In addition, the said content can also be computed from the compounding quantity at the time of mix
  • the antifouling composition of the present invention is the ratio of the molar amount of the component (A) to the molar amount of the component (C) in the relationship between the component (A) and the component (C) [(A) / (C)].
  • (Molar ratio) is not particularly limited and is preferably 1.0 or more.
  • the [(A) / (C)] (molar ratio) is preferably 70.0 or less.
  • the antifouling composition of the present invention is an antifouling composition that satisfies the following condition (II) in relation to the component (B) and the component (C).
  • the water contact angle of the antifouling layer formed from the antifouling composition is reduced due to the extreme decrease in the proportion of the alkyl group represented by R 2 in the component (B), resulting in water repellency.
  • the [(B) / ⁇ (B) + (C) ⁇ ] (molar ratio) is preferably 0.025 or more, more preferably 0.035 or more, and further preferably 0.045 or more. More preferably, it is 0.050 or more.
  • the upper limit of the [(B) / ⁇ (B) + (C) ⁇ ] (molar ratio) is not particularly limited, and the [(B) / ⁇ (B) + (C) ⁇ ] (molar ratio) is , Preferably 0.995 or less, more preferably 0.990 or less, still more preferably 0.980 or less, and still more preferably 0.950 or less.
  • antifouling composition of this invention contains (B) component and (C) component as a trifunctional silane type compound so that the said conditions (I) and conditions (II) may be satisfy
  • filled, antifouling property A high surface hardness and a low coefficient of friction of the antifouling layer formed from the composition can be compatible.
  • the weather resistance improvement of the antifouling layer formed from an antifouling composition can be expected by including the component (C).
  • the antifouling composition of the present invention is the component (A), the component (B) and the component (C) in the relationship between the component (A) and the component (C) with respect to the total molar amount of the component (A).
  • the amount ratio [(A) / ⁇ (B) + (C) ⁇ ] (molar ratio) is preferably 0.50 or more, more preferably 0.90 or more. Further, the [(A) / ⁇ (B) + (C) ⁇ ] (molar ratio) is preferably 25.00 or less, more preferably 20.00 or less.
  • the antifouling composition of the present invention contains a metal catalyst as the component (D) together with the components (A) to (C).
  • the metal catalyst is not included, the condensation reaction of the component (A), the component (B) and the component (C) cannot be effectively promoted, and the antifouling layer formed from the antifouling composition is cured. The sex cannot be improved sufficiently. Further, in the case of the antifouling composition not containing the component (D), the curing reaction cannot sufficiently proceed at a relatively low temperature (130 ° C. or lower).
  • the antifouling when it is desired to form an antifouling layer formed from the antifouling composition on a substrate having low heat resistance such as a vinyl chloride resin, the antifouling is prevented at a low temperature that can suppress the thermal shrinkage of the substrate. If an attempt is made to form a dirty layer, the curability of the antifouling layer may be insufficient. On the other hand, in order to sufficiently advance the curing reaction, there is a risk that the base material may undergo thermal shrinkage when attempting to cure at a relatively high temperature (over 130 ° C.).
  • the metal catalyst is preferably a metal catalyst that does not require light irradiation for the expression of catalytic action.
  • the said "metal catalyst which does not require light irradiation for catalytic action expression” means the catalytic action with respect to the condensation reaction with said (A) component, (B) component, and (C) component. It refers to a metal catalyst that does not require light irradiation to develop.
  • light irradiation is required for the expression of a catalytic action such as titanium oxide (TiO 2 ) and zinc oxide (ZnO), which causes oxidation and reduction reactions by generating electrons and holes by light irradiation. What is commonly called photocatalyst is excluded.
  • the antifouling layer contains the above-mentioned “metal catalyst that does not require light irradiation for the expression of the catalytic action”, it is possible to avoid problems that may occur when a photocatalyst is used.
  • the troubles that may occur when using the photocatalyst are, for example, a decrease in water repellency due to an increase in the surface roughness of the antifouling layer due to the fact that the photocatalyst itself is a solid substance, There are problems such as a decrease in water repellency due to the effect of imparting hydrophilicity and a decrease in durability of the antifouling layer by promoting hydrolysis of the polymer of the silane compound.
  • the metal catalyst is preferably at least one selected from the group consisting of a titanium catalyst, a zirconium catalyst, a palladium catalyst, a tin catalyst, an aluminum catalyst, and a zinc catalyst.
  • the titanium-based catalyst is preferably a compound other than a photocatalyst containing a titanium atom, for example, titanium alkoxide, titanium chelate, titanium acylate, etc., including titanium hydroxide, acetate, carbonate, It may be sulfate, nitrate, chloride or the like.
  • titanium alkoxide include titanium tetraisopropoxide, titanium tetranormal butoxide, titanium butoxide dimer, titanium tetra-2-ethylhexoxide, and the like.
  • titanium chelate examples include titanium acetylacetonate such as titanium diisopropoxybis (acetylacetonate) and titanium tetraacetylacetonate; titanium ethylacetoacetate such as titanium diisopropoxybis (ethylacetoacetate); Titanium triethanolamate such as propoxybis (triethanolaminate); titanium tetraoctylene glycolate, titanium dioctyloxybis (octylene glycolate), titanium di-2-ethylhexoxybis (2-ethyl-3- And titanium octylene glycolate such as hydroxy hexoxide); titanium lactate, titanium lactate ammonium salt and the like.
  • titanium acylate examples include polyhydroxy titanium stearate.
  • the zirconium-based catalyst is preferably a compound other than a photocatalyst containing a zirconium atom, and examples thereof include zirconium alkoxide, zirconium chelate, zirconium acylate, and the like, zirconium hydroxide, acetate, carbonate, It may be sulfate, nitrate, chloride or the like.
  • zirconium alkoxide include zirconium tetranormal propoxide, zirconium tetranormal butoxide and the like.
  • zirconium chelate examples include zirconium acetylacetonate such as zirconium tributoxy monoacetylacetonate and zirconium tetraacetylacetonate; zirconium ethylacetoacetate such as zirconium dibutoxybis (ethylacetoacetate); zirconyl chloride compound and zirconium lactate ammonium. Examples include salts. Examples of the zirconium acylate include a zirconium octylate compound and zirconium stearate.
  • the palladium-based catalyst is preferably a compound other than a photocatalyst containing a palladium atom, and examples thereof include palladium, palladium chloride, palladium hydroxide, palladium carbon catalyst (Pd / C) and the like.
  • the tin-based catalyst is preferably a compound other than a photocatalyst containing a tin atom.
  • examples thereof include an organic tin compound such as dimaleate, dioctyltin mercaptide, and dioctyltin thiocarboxylate, or an inorganic tin compound.
  • the aluminum-based catalyst is preferably a compound other than a photocatalyst containing an aluminum atom, and examples thereof include an aluminum acetoacetate complex and an aluminum acetylacetonate complex.
  • aluminum acetoacetate complexes include diisopropoxy aluminum monooleyl acetoacetate, monoisopropoxy aluminum bis oleyl acetoacetate, monoisopropoxy aluminum monooleate monoethyl acetoacetate, diisopropoxy aluminum monolauryl acetoacetate, Examples thereof include isopropoxyaluminum monostearyl acetoacetate, diisopropoxyaluminum monoisostearyl acetoacetate, monoisopropoxyaluminum mono-N-lauroyl- ⁇ -alanate monolauryl acetoacetate, and aluminum trisacetylacetonate.
  • aluminum acetylacetonate complexes include monoacetylacetonate aluminum bis (isobutyl acetoacetate) chelate, monoacetylacetonate aluminum bis (2-ethylhexyl acetoacetate) chelate, monoacetylacetonate aluminum bis (dodecylacetoacetate) Chelate, monoacetylacetonate aluminum bis (oleyl acetoacetate) chelate, and the like.
  • the zinc-based catalyst is preferably a compound other than a photocatalyst containing a zinc atom, such as zinc-chromium oxide, zinc-aluminum oxide, zinc-aluminum-chromium oxide, zinc-chromium-manganese oxidation. Products, zinc-iron oxide, zinc-iron-aluminum oxide, and the like.
  • the metal catalyst you may use individually or in combination of 2 or more types. In addition, it effectively promotes the condensation reaction between the silane compounds, improves the curability of the antifouling layer formed from the antifouling composition, and cures even at relatively low temperatures (130 ° C. or lower). From the viewpoint of making the antifouling composition capable of proceeding, it is preferable to contain at least the titanium-based catalyst.
  • the titanium catalyst is preferably a titanium chelate, more preferably titanium ethyl acetoacetate, titanium acetylacetonate or titanium octylene glycolate, still more preferably titanium ethyl acetoacetate, and titanium diisopropoxybis (ethyl acetoacetate). Even more preferred.
  • Content of (D) component in antifouling composition is a viewpoint which improves the sclerosis
  • the content is preferably 50.000 mol% or less, more preferably 30.000 mol% or less, still more preferably 20.000 mol% or less, still more preferably 10.000 mol% or less, and even more preferably. It is 6.000 mol% or less, more preferably 3.000 mol% or less.
  • the said content can also be computed from the compounding quantity at the time of mix
  • the antifouling composition of the present invention preferably further contains an acid catalyst as the component (E) from the viewpoint of further improving the curability of the antifouling layer formed from the antifouling composition.
  • an acid catalyst as the component (E) from the viewpoint of further improving the curability of the antifouling layer formed from the antifouling composition.
  • hydrochloric acid formic acid, sulfuric acid, methanesulfonic acid, odorous acid, p-toluenesulfonic acid
  • said acid catalyst you may use individually or in combination of 2 or more types.
  • the content of the component (E) in the antifouling composition is (A), (B) and (C )
  • the total of 100 mol% of the components is preferably 0.010 mol% or more, more preferably 0.030 mol% or more, still more preferably 0.050 mol% or more, still more preferably 0.060 mol% or more. It is. And the said content becomes like this. Preferably it is 1.000 mol% or less, More preferably, it is 0.500 mol% or less, More preferably, it is 0.100 mol% or less, More preferably, it is 0.075 mol% or less.
  • the said content can also be computed from the compounding quantity at the time of mix
  • the antifouling composition may contain other additives in addition to the components (A) to (E) described above as long as the effects of the present invention are not impaired.
  • examples of other additives include a resin component, a curing agent, an anti-aging agent, a light stabilizer, a flame retardant, a conductive agent, an antistatic agent, and a plasticizer.
  • the content of each of these additives is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, still more preferably 0 to 5% by mass, and still more based on the total amount of the antifouling composition.
  • the content is preferably 0 to 2% by mass.
  • the total content of the (A) component, (B) component, (C) component, and (D) component in the antifouling composition is the total amount of the antifouling composition (solid content: 100% by mass). Is preferably 50% by mass or more, more preferably 65% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, and even more preferably 99%. It is at least mass%, and preferably at most 100 mass%. In addition, the said content can also be computed from the compounding quantity at the time of mix
  • the total content of the (A) component, (B) component, (C) component, (D) component and (E) component in the antifouling composition is the total amount (solid content) of the antifouling composition. 100% by mass), preferably 50% by mass or more, more preferably 65% by mass or more, further preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, more More preferably, it is 99 mass% or more, and preferably 100 mass% or less. Further, the content is more preferably 100% by mass. In addition, the said content can also be computed from the compounding quantity at the time of mix
  • the object to which the antifouling composition of the present invention is applied is not particularly limited as long as antifouling property is required, but glass, metal, alloy, semiconductor, rubber, cloth, plastic, ceramics, It can be suitably used for wood, paper, fiber and the like, and can be more suitably used for glass and metal. Moreover, it can be used suitably also for a metal oxide film or a resin coating surface.
  • coating the said antifouling composition to a to-be-coated body it melt
  • organic solvent examples include methanol, ethanol, propanol, butanol, isopropyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, toluene, mineral spirit, and the like.
  • the method for applying the antifouling composition to the substrate is not particularly limited. For example, spin coating, spray coating, bar coating, knife coating, roll knife coating, roll coating, Examples include a blade coating method, a die coating method, and a gravure coating method.
  • FIG. 1 is a cross-sectional view of an antifouling sheet having a substrate, which is an example of an embodiment according to the antifouling sheet of the present invention.
  • seat which has a base material the antifouling sheet
  • FIG. 2 is a cross-sectional view of an antifouling sheet having no substrate, which is an example of an embodiment according to the antifouling sheet of the present invention.
  • the antifouling sheet having no base material for example, as shown in FIG. 2A, the antifouling sheet 2a has a configuration in which the antifouling layer 11 is sandwiched between two release materials 14 and 14 ′. Is mentioned.
  • the antifouling sheet 2b is further provided with an adhesive layer 13 between the antifouling layer 11 and the release material 14 ′. Also good.
  • the antifouling layer of the antifouling sheet of the present invention is formed from the above-described antifouling composition of the present invention.
  • the thickness of the antifouling layer is preferably 0.001 ⁇ m or more, more preferably 0.005 ⁇ m or more, still more preferably 0.01 ⁇ m or more, still more preferably 0.05 ⁇ m or more, and still more preferably 0.10 ⁇ m or more. It is.
  • the thickness is preferably 40 ⁇ m or less, more preferably 25 ⁇ m or less, still more preferably 15 ⁇ m or less, still more preferably 5.0 ⁇ m or less, still more preferably 1.0 ⁇ m or less, and even more preferably 0.80 ⁇ m or less. It is.
  • the surface hardness of the antifouling layer is preferably 0.8 GPa or more, more preferably 1.0 GPa or more, still more preferably 1.3 GPa or more, still more preferably 1.5 GPa or more, still more preferably 2.0 GPa or more, Still more preferably, it is 2.5 GPa or more, More preferably, it is 2.8 GPa or more.
  • the surface hardness is preferably 40 GPa or less, more preferably 30 GPa or less.
  • the water contact angle of the antifouling layer is preferably 70 ° or more, more preferably 80 ° or more, still more preferably 95 ° or more, and still more preferably 100 ° or more.
  • the water contact angle is preferably 179 ° or less, more preferably 170 ° or less, and still more preferably 160 ° or less.
  • the water sliding angle of the antifouling layer is preferably 25 ° or less, more preferably 20 ° or less.
  • the water sliding angle is preferably 0.001 ° or more, more preferably 0.002 ° or more.
  • the static friction coefficient of the antifouling layer is preferably 0.33 or less, more preferably 0.30 or less, still more preferably 0.25 or less, and still more preferably 0.20 or less.
  • the static friction coefficient is preferably 0.01 or more, more preferably 0.05 or more.
  • the dynamic friction coefficient of the antifouling layer is preferably 0.34 or less, more preferably 0.32 or less, still more preferably 0.26 or less, and still more preferably 0.23 or less.
  • the said dynamic friction coefficient becomes like this. Preferably it is 0.01 or more, More preferably, it is 0.05 or more.
  • said thickness, surface hardness, water contact angle, water sliding angle, static friction coefficient, and dynamic friction coefficient can be measured by the method as described in the Example mentioned later, respectively.
  • Examples of the substrate used in one aspect of the antifouling sheet of the present invention include a paper substrate, a resin film, a resin sheet, a substrate obtained by laminating a paper substrate with a resin, a glass sheet, a metal foil, and a metal sheet. And can be appropriately selected according to the use of the antifouling sheet.
  • Examples of the paper constituting the paper substrate include thin paper, medium quality paper, high quality paper, impregnated paper, coated paper, art paper, sulfuric acid paper, glassine paper and the like.
  • the resin constituting the resin film or resin sheet examples include polyolefin resins such as polyethylene and polypropylene; polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, etc. , Ethylene-methacrylic acid copolymer vinyl resin; polyester resin such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate; polystyrene; acrylonitrile-butadiene-styrene copolymer; cellulose triacetate; polycarbonate; polyurethane; Examples thereof include urethane resins such as polyurethane.
  • polyolefin resins such as polyethylene and polypropylene
  • polyvinyl chloride, polyvinylidene chloride polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer,
  • Examples of the base material obtained by laminating a paper base material with a resin include laminated paper obtained by laminating the paper base material with a thermoplastic resin such as polyethylene.
  • a resin film or a resin sheet is preferable, a resin film or a resin sheet made of a polyester resin is more preferable, and a resin film or a resin sheet made of polyethylene terephthalate (PET) is more preferable.
  • PET polyethylene terephthalate
  • limiting in particular as a metal foil or a metal sheet For example, the metal foil or metal sheet which consists of various metals, such as aluminum, nickel, stainless steel, copper, titanium, or tungsten, is mentioned.
  • a substrate may be used.
  • a polyester-type resin, a urethane type resin, a polyester urethane type resin, an acrylic resin etc. are mentioned, for example, These resin may be used individually or in combination of 2 or more types. .
  • a weather resistance layer further provided with a weather resistant layer made of a polymer ultraviolet absorber on the surface of the base material or the surface of the base material with a primer layer.
  • a substrate with a layer (which may have a primer layer between the weather-resistant layer and the substrate) may be used.
  • the polymer ultraviolet absorber has a structure in which an ultraviolet absorption skeleton is covalently bonded in a polymer structure, and preferably has a weight average molecular weight of 5,000 or more, more preferably 10,000 or more. is there.
  • seat of this invention is a resin film or a resin sheet
  • these resin films or resin sheets are needed as needed.
  • a surface treatment such as an oxidation method or a concavo-convex method may be applied to the surface.
  • the oxidation method is not particularly limited, and examples thereof include a corona discharge treatment method, a plasma treatment method, chromic acid oxidation (wet), flame treatment, hot air treatment, and ozone / ultraviolet irradiation treatment.
  • corrugated method For example, a sandblasting method, a solvent processing method, etc.
  • the thickness of the substrate is appropriately set according to the use of the antifouling sheet, but is preferably 10 to 250 ⁇ m, more preferably 15 to 200 ⁇ m, and still more preferably 20 to 150 ⁇ m from the viewpoints of handleability and economy. It is.
  • the base material used in the present invention further contains an ultraviolet absorber other than the above-described polymer ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a slip agent, an antiblocking agent, a colorant and the like. May be.
  • a release sheet subjected to double-sided release treatment, a release sheet subjected to single-sided release treatment, or the like is used, and the release agent is formed on the base material for the release material.
  • coated are mentioned.
  • a base material for the release material for example, a paper base material, a resin film, a resin sheet, and a base material obtained by laminating a paper base material with a resin, which can be used as a base material of one aspect of the antifouling sheet of the present invention Etc.
  • the release agent examples include rubber elastomers such as silicone resins, olefin resins, isoprene resins, and butadiene resins, long chain alkyl resins, alkyd resins, and fluorine resins.
  • the thickness of the release material is not particularly limited, and is preferably 10 to 200 ⁇ m, more preferably 25 to 150 ⁇ m.
  • the two release materials may be the same as or different from each other.
  • the adhesive constituting the adhesive layer can be appropriately selected according to the use of the antifouling sheet.
  • Specific adhesives include, for example, acrylic adhesives, urethane adhesives, silicone adhesives, rubber adhesives, polyester adhesives, and curable adhesives that are cured by energy rays such as ultraviolet rays. It is done.
  • These pressure-sensitive adhesives may be used alone or in combination of two or more.
  • the thickness of the pressure-sensitive adhesive layer is not particularly limited, and is preferably 1 to 100 ⁇ m, more preferably 5 to 80 ⁇ m.
  • Step (1) Step (A) for preparing an antifouling composition containing the following components (A) to (D) and satisfying the following conditions (I) and (II): Component (A): Si (OR 1 ) p (X 1 ) 4-p (a)
  • R 1 represents an alkyl group having 1 to 6 carbon atoms
  • X 1 represents a halogen atom.
  • p represents an integer of 0 to 4.
  • R 2 represents an alkyl group having 6 to 14 carbon atoms.
  • R 3 represents an alkyl group having 1 to 6 carbon atoms, and
  • X 2 represents a halogen atom. If R 3 and X 2 there are a plurality, the plurality of R 3 and X 2 are either identical to one another or may be different.
  • q represents an integer of 0 to 3.
  • Component (D) Metal catalyst condition (I): Ratio of molar amount of component (A) to molar amount of component (B) [(A) / (B)] (molar ratio) is 1.4 or more ( II): Ratio of molar amount of component (B) to total molar amount of component (B) and component (C) [(B) / ⁇ (B) + (C) ⁇ ] (molar ratio) is 0.020.
  • Step (2) Step of applying the antifouling composition onto a substrate or a release material and drying to form an antifouling layer
  • the antifouling composition of this invention when apply
  • the organic solvent include methanol, ethanol, propanol, butanol, isopropyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, toluene and the like.
  • the coating method include spin coating, spray coating, bar coating, knife coating, roll knife coating, roll coating, blade coating, die coating, and gravure coating.
  • the drying temperature is preferably 10 to 130 ° C, more preferably 20 to 120 ° C, still more preferably 40 to 110 ° C, and still more preferably 50 to 95 ° C. is there.
  • a release material may be further laminated on the formed antifouling layer in order to protect the surface of the antifouling layer during storage.
  • the antifouling sheet 1b in FIG. 1 (b) or the antifouling sheet 2b in FIG. 2 (b) is obtained by laminating the adhesive layer formed on another release material on the formed antifouling layer. Such an antifouling sheet with an adhesive layer can also be produced.
  • Examples 1 to 21 and Comparative Examples 1 to 5 (1) Preparation of antifouling composition (A) component, (B) component and (C) component are mix
  • ⁇ (C) component trifunctional silane compound represented by general formula (c)>
  • Component (D) Metal-based catalyst> "Titanium catalyst”: Titanium diisopropoxybis (ethyl acetoacetate) [manufactured by Matsumoto Fine Chemical Co., Ltd., product name "Orgatechs TC-750"].
  • the thickness of the antifouling layer is J. A. Measurement was performed with a spectroscopic ellipsometer (product name “M-2000”) manufactured by Woollam.
  • ⁇ Stain condition of antifouling layer> The surface of the antifouling layer of the antifouling sheet prepared in each Example and each Comparative Example was visually observed, and the surface state of the antifouling layer was evaluated according to the following criteria. A: Transparent. B: Slight cloudiness was confirmed. C: Cloudy and no longer transparent. In addition, about what was evaluation of the surface state of the pollution protection layer was "C", since it cannot endure use, evaluation other than the curability evaluation of a pollution protection layer shown below is not performed.
  • ⁇ Curability of antifouling layer> The surface of the antifouling layer of the antifouling sheet produced in each Example and each Comparative Example was visually observed after rubbing 20 times with a finger, and the curability of the antifouling layer was observed according to the following criteria. Evaluated. -A: A change was not seen compared with before rubbing with a finger. B: Discolored slightly white, but acceptable. C: Discolored white. -D: The antifouling layer could not be formed because the coating film made of the antifouling composition was not cured. In addition, about what was evaluation of curability of an antifouling layer was "C" or "D", since it cannot endure use, each evaluation shown below is not performed.
  • the water contact angle of the antifouling layer was measured using the fully automatic contact angle measuring device (product name “DM-701”) manufactured by Kyowa Interface Science Co., Ltd. About the antifouling layer surface, it measured as a contact angle with respect to 2 microliters of water.
  • ⁇ Water sliding angle of antifouling layer> The antifouling sheet produced in each example and each comparative example was placed on a sample table (glass plate) with an inclination angle of 0 ° by water filling. Next, 14 ⁇ L of pure water was dropped on the antifouling layer surface of the antifouling sheet to form droplets, and then the sample stage when the receding angle of the liquid droplets moved when the sample stage was tilted. The slant angle was defined as the water sliding angle.
  • ⁇ Friction coefficient of antifouling layer> Based on JIS K7312, it tested using the universal tensile tester Tensilon by A & D Co., Ltd.
  • a sample prepared from the antifouling sheet prepared in each of Examples and Comparative Examples was attached to a weight of a square and smooth metal plate (200 g) having a side of 63.5 mm, and a polyethylene terephthalate film (product of Toray Industries, Inc.)
  • the static friction coefficient and the dynamic friction coefficient with respect to the name “Lumirror T-60” (thickness 50 ⁇ m) were measured.
  • the antifouling layers formed from the antifouling compositions of Examples 1 to 19 had good surface conditions and curability. It was confirmed that the water contact angle was large, the water sliding angle was small, and the water repellency and water sliding property were excellent. Moreover, the surface hardness was high, the friction coefficient was low, and all the characteristics were good. Moreover, although the antifouling layer formed from the antifouling compositions of Examples 20 and 21 was inferior in curability to other examples, it was acceptable for practical use. The surface condition of the antifouling layer was good. It was also confirmed that the water contact angle was large, the water sliding angle was small, and the water repellency and water sliding property were excellent. Also, the surface hardness was acceptable and the friction coefficient was low and good.
  • the antifouling layer formed from the antifouling compositions of Comparative Examples 1 and 2 is an alkyl group represented by R 2 in the general formula (b) representing the component (B). Since the number of carbons in the sample exceeded 14, the surface condition and curability were inferior. Therefore, it is judged that the antifouling sheet having these antifouling layers cannot be used, and no evaluation other than the evaluation concerning the surface state and the curability is performed. Moreover, since the antifouling layer formed from the antifouling composition of Comparative Example 3 did not satisfy the condition (I), the surface hardness was remarkably inferior. Moreover, since the antifouling layer formed from the antifouling compositions of Comparative Examples 4 and 5 did not satisfy the condition (II), the friction coefficient was high and the friction characteristics were inferior.
  • the antifouling layer formed from the antifouling composition of the present invention has a good surface state and curability, good water repellency and water slidability, and has a high surface hardness and a low friction coefficient. Therefore, the antifouling sheet of the present invention having the antifouling layer is, for example, windshield glass for buildings, automobile windows, vehicles, aircraft, ships, etc., water tanks, ship bottom windows, marine organisms attached to the ship bottom. Prevents the adhesion of water droplets, scratches, dirt, and other items that obstruct the field of view, such as prevention films, road panels such as soundproof walls, mirrors installed in bathrooms, glass containers, glass ornaments, etc. Therefore, it is suitable as an antifouling sheet.
  • water repellency and water slidability that can efficiently slid water droplets and snow falling on windshield glass of automobile window glass, vehicles, aircraft, ships, etc., and reduced surface adhesion due to excellent surface hardness and friction characteristics Is more suitable when used in applications where it is required to be used in an environment.

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Abstract

La présente invention concerne une composition antisalissure qui comprend un composé à base de silane tétrafonctionnel ayant une structure spécifique comme composant (A), des composés à base de silane trifonctionnel ayant respectivement différentes structures spécifiques comme composant (B) et composant (C), et un catalyseur métallique comme composant (D) et qui satisfait à l'exigence (I) : le rapport entre la quantité molaire du composant (A) et la quantité molaire du composant (B), (A)/ (B) (par mole), étant de 1,4 ou plus et à l'exigence (II) : le rapport entre la quantité molaire du composant (B) et la quantité molaire totale du composant (B) et du composant (C), (B)/ {(B) + C)} (par mole), étant de 0,020 ou plus ; une feuille antisalissure comprenant une couche antisalissure formée à partir de la composition anti-salissure ; et un procédé de production de la feuille antisalissure.
PCT/JP2016/070700 2015-07-16 2016-07-13 Composition antisalissure, feuille antisalissure et procédé de production d'une feuille antisalissure WO2017010517A1 (fr)

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JP2016564346A JP6111004B1 (ja) 2015-07-16 2016-07-13 防汚性組成物、防汚性シート、及び防汚性シートの製造方法
EP16824497.8A EP3323865B1 (fr) 2015-07-16 2016-07-13 Composition antisalissure, feuille antisalissure et procédé de production d'une feuille antisalissure
US15/744,464 US20180201796A1 (en) 2015-07-16 2016-07-13 Antifouling composition, antifouling sheet, and process for producing antifouling sheet
CN201680041456.XA CN107849394B (zh) 2015-07-16 2016-07-13 防污性组合物、防污片、及防污片的制造方法
KR1020187001094A KR102632023B1 (ko) 2015-07-16 2016-07-13 방오성 조성물, 방오성 시트 및 방오성 시트의 제조 방법

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WO2018164223A1 (fr) * 2017-03-08 2018-09-13 ホヤ レンズ タイランド リミテッド Composition filmogène, article revêtu d'un film, et procédé de production d'un article revêtu d'un film
CN110392722A (zh) * 2017-03-10 2019-10-29 琳得科株式会社 拒液性组合物、拒液片及它们的制造方法
JP2021152090A (ja) * 2020-03-24 2021-09-30 大日本塗料株式会社 塗料組成物

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EP3323865A4 (fr) 2019-01-23
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